Synthesis and properties of copolyesters of p,p′‐bibenzoic acid,dimer acid,and alkylene glycol

Copolyesters of p,p′‐bibenzoic acid, dimer acid, and an alkylene glycol are prepared by melt polycondensation of of dimethyl p,p′‐bibenzoate, dimer acid, and an alkylene glycol. The copolyesters are characterized by the inherent viscosity, FTIR, proton NMR, DSC, polarized microscopy, and X‐ray diffraction. The polymer composition and sequence distribution of the copolyesters can be seen from the NMR spectra. The copolyesters exhibit a degree of randomness of about 1, indicating that they are random copolymers. The glass‐transition temperature (T_g) and the melting point (T_m) of the copolyesters are found from the DSC heating curves. When the content of the flexible dimer acid unit increases, the T_g of the copolyesters decreases significantly. The copolymerization effect decreases the crystallinity and the T_m of the copolyesters. It can be seen from the DSC, polarized microscopy, and X‐ray diffraction data that some copolyesters derived from 1,6‐hexanediol and 1,5‐pentanediol exhibit a monotropic smectic phase. As the molar content of the dimer acid unit increases, the isotropic–mectic transition temperature and the smectic order decreases significantly. The liquid crystallinity is completely destroyed at certain molar contents of the dimer acid unit. The smectic order of the copolyesters derived from 1,6‐hexanediol is significantly higher than that of the copolyesters derived from 1,5‐pentanediol, and it is described as an odd–even effect. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 750–758, 2003     

Synthesis and properties of TLCPs with 2,6‐naphthalene‐based mesogen,polymethylene spacer,and nonlinear 4,4′‐thiodiphenyl links

A series of new thermotropic main‐chain liquid crystalline copolyesters were prepared by polycondensation of 2,6‐naphthalenedicarbonyl chloride, 4,4′‐thiodiphenol, and α,ω‐alkanediols (n = 4–10) in diphenyl ether at 200°C. Thermal transition behaviors of these copolyesters were investigated by differential scanning calorimetry. Moreover, their thermal stabilities and mesomorphic textures were studied by thermogravimetric analysis and polarizing optical microscopy, respectively. Corresponding model compounds with terminal mesogenic units and central polymethylene spacers were also synthesized for comparison. Both copolymers and model compounds exhibit odd–even dependency of melting temperatures, transition enthalpy (ΔH_m), and entropy (ΔS_m) on the number of methylene units in the spacer. However, the odd–even effects in model compounds are much more distinctive. Nematic mesophases are the only texture observed in melts, except the model compounds with longer methylene units (n = 8, 10), in which smectic mesophases can be observed. The T_m values of the copolyesters (TDP/HD = 1/1) are between 233 and 259°C, depending on spacer length. The initial decomposition temperatures of the copolyesters are above 419°C under N₂ atmosphere. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1536–1546, 2002     

Synthesis and properties of poly(alkylene p,p′-bibenzoate-co-adipate)s

Various poly(alkylene p,p′-bibenzoate-co-adipate)s were prepared by melt polycondensation of dimethyl-p,p′-bibenzoate, adipic acid, and an alkylene glycol. The copolyesters were characterized by inherent viscosity, FTIR, proton NMR, DSC, polarized microscopy, and X-ray diffraction. The polymer composition and sequence distribution of the copolyesters can be seen from NMR spectra. The copolyesters exhibit a degree of randomness of about 1, indicating that they are random copolymers. From the DSC data, the glass transition temperature (T_g) and melting point (T_m) of the copolyesters can be detected. When the content of the flexible adipate unit increases, the T_g of copolyesters decreases significantly. The type of alkylene glycol used also affects the T_g to some extent. The copolymerization effect decreases crystallinity and the T_m of the copolyesters. The DSC, polarized microscopy, and X-ray diffraction data show that some copolyesters derived from 1,6-hexanediol exhibit a monotropic smectic phase. As the molar fraction of adipate unit in diacid units, x, is more than 0.4, the liquid crystallinity is completely destroyed. © 1997 John Wiley & Sons, Inc. J Appl Polm Sci 65:893–900, 1997     

Amorphous copolyesters based on 1,3/1,4‐cyclohexanedimethanol: Synthesis,characterization and properties

Two series of amorphous copolyesters, PETGN and PETGS, were synthesized by the copolymerization of 2,6‐naphthalene dicarboxylic acid (NDA) (0–40%), succinic acid (SA) (0–40%), 1,3/1,4‐cyclohexanedimethanol (1,3/1,4‐CHDM) (10–50%), ethylene glycol (EG), and terephthalic acid (TPA). The compositions and molecular weights of the copolyesters were determined by ¹H NMR spectroscopy and viscometry, respectively. The thermal behaviors were studied over the entire range of copolymer compositions, using DSC and TGA. The optical characteristics, heat‐shrinkable effects and tensile properties of these polymers were also determined. Experimental results indicated that the thermal, optical, tensile, and shrinkage properties of PETGN and PETGS were functions of NDA or SA content. DSC and X‐ray analysis demonstrated that both PETGN and PETGS series were amorphous. Incorporating NDA and SA influenced the T_g values of those polymers, from about 37°C for PETG₃₀S₄₀ to 89°C for PETG₃₀N₄₀. Furthermore, the shrinkage of these amorphous copolyesters was more than 40% when the heating temperature was higher than the corresponding T_g. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Biodegradable poly(ethylene succinate) blends and copolymers containing minor amounts of poly(butylene succinate)

Poly(ethylene succinate) (PES), poly(butylene succinate) (PBS), and PES‐rich copolyesters were synthesized using an effective catalyst, titanium tetraisopropoxide. PES was blended with minor amounts of PBS for the comparison. The compositions of the copolyesters and the blends were determined from NMR spectra. Their thermal properties were studied using a differential scanning calorimeter (DSC), a temperature modulated DSC (TMDSC), and a thermogravimetric analyzer. No significant difference exists among the thermal stabilities of these polyesters and blends. For the blends, the reversible curves of TMDSC showed a distinct glass‐rubber transition temperature (T_g), however, the variation of the T_g values with the blend compositions was small. Isothermal crystallization kinetics and the melting behavior after crystallization were examined using DSC. Wide‐angle X‐ray diffractograms (WAXD) were obtained for the isothermally crystallized specimens. The results of DSC and WAXD indicate that the blends have a higher degree of crystallinity and a higher melting temperature than those of the corresponding copolymers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Morphology and texture development of uniaxially stretched poly(ethylene naphthalene‐2,6‐dicarboxylate)

The texture development of PEN films with different semicrystalline morphologies have been studied by X‐ray diffraction. These different structures have been obtained by uniaxially stretching PEN amorphous films at 100 and 160°C (below and above T_g) at different drawing ratios. Samples have also been characterized by DSC to determine the crystallinity ratios, the crystallization, and melting temperatures. To define the orientation of crystallites in the oriented samples, pole figures have been constructed, as a function of temperature and drawing ratio (DR) in the range 1.5–4. In the range from DR = 2 to 4 the orientation is clearly uniplanar‐axial. At T_draw = 100°C the crystallinity shown by DSC analysis is higher than the sample stretched at 160°C. The orientation is also higher when samples are stretched at 100°C. The naphthalene rings mainly stay in the plane of the film with a lower fraction perpendicular to the plane of the film. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 395–401, 2007     

Segmented copolymers of uniform tetra‐amide units and poly(phenylene oxide) by direct coupling

Segmented copolymers with telechelic poly(2,6‐dimethyl‐1,4‐phenylene ether) (PPE) segments and crystallizable bisester tetra‐amide units (two‐and‐a‐half repeating unit of nylon‐6,T) were studied. The copolymers were synthesized by reacting bifunctional PPE with hydroxylic end groups with an average molecular weight of 3500 g/mol and bisester tetra‐amide units via an ester polycondensation reaction. The bisester tetra‐amide units had phenolic ester groups. By replacing part of the bisester tetra‐amide units with diphenyl terephthalate units (DPT), the concentration of tetra‐amide units in the copolymer was varied from 0 to 11 wt%. Polymers were also prepared from bifunctional PPE, DPT, and a diaminediamide (6T6‐diamine). The thermal and thermal mechanical properties were studied by DSC and DMA and compared with a copolymer with flexible spacer groups between the PPE and the T6T6T. The copolymers had a high T_g of 180–200°C and a melting temperature that increased with amide content of 220–265°C. The melting temperature was sharp with monodisperse amide segments. The T_m – T_c was 39°C, which suggests a fast, but not very fast, crystallization. The crystallinity of the amide was ～ 20%. The copolymers are semicrystalline materials with a high T_g and a high T_g/T_m ratio (> 0.8). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 512–518, 2007     

Composition,thermal properties,and biodegradability of a new biodegradable aliphatic/aromatic copolyester

A series of new aliphatic/aromatic copolyesters [poly(hexylene terephthalate‐co‐hexylene adipate) (PHTA)] were synthesized on the bases of 1,6‐hexanediol, adipic acid, and dimethyl terephthalate and characterized by gel permeation chromatography, ¹H‐NMR, wide‐angle X‐ray diffraction (WAXD), differential scanning calorimetry (DSC), and compost testing. ¹H‐NMR results show that the compositions of the copolyesters were in accordance with the feed molar ratios. The WAXD patterns indicated that the crystal structures of the PHTA copolyesters were determined by the dominant crystal units, and the copolyesters became less crystallizable, even amorphous, with increasing comonomer content. The DSC curves showed that the glass‐transition temperatures (T_g′s) of the PHTA copolyesters decreased linearly, and both the melting temperature (T_m) and heat of fusion decreased first and then increased with increasing hexylene adipate unit content. Under compost conditions, PHTA copolyesters with less than 60 mol % aromatic units were biodegradable. Particularly, compared with the copolyester poly(butylene terephthalate‐co‐butylene adipate), the PHTA copolyester with the same aliphatic/aromatic composition possessed a lower T_g and T_m and better biodegradability. Additionally, the biodegradability of the copolyesters could be predicted by the number‐average sequence length of aromatic units, T_g, and the temperature difference between T_m and the temperature at which biodegradation took place. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Starch‐g‐polycaprolactone copolymerization using diisocyanate intermediates and thermal characteristics of the copolymers

Starch‐g‐polycaprolactone copolymers were prepared by two‐step reactions. The diisocyanate‐terminated polycaprolactone (NCO–PCL) was prepared by introducing NCO on both hydroxyl ends of PCL using diisocyanates (DI) at a molar ratio between PCL and DI of 2:3. Then, the NCO–PCL was grafted onto corn starch at a weight ratio between starch and NCO–PCL of 2:1. The chemical structure of NCO–PCL and the starch‐g‐PCL copolymers were confirmed by using FTIR and ¹³C‐NMR spectrometers, and then the thermal characteristics of the copolymers were investigated by DSC and TGA. By introducing NCO to PCL (M_n : 1250), the melting temperature (T_m ) was reduced from 58 to 45°C. In addition, by grafting the NCO–PCL (35–38%) prepared with 2,4‐tolylene diisocyanate (TDI) or 4,4‐diphenylmethane diisocyanate (MDI) onto starch, the glass transition temperatures (T_g 's) of the copolymers were both 238°C. With hexamethylene diisocyanate (HDI), however, T_g was found to be 195°C. The initial thermal degradation temperature of the starch‐g‐PCL copolymers were higher than that of unreacted starch (320 versus 290°C) when MDI was used, whereas the copolymers prepared with TDI or HDI underwent little change. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 986–993, 2000     

Synthesis and characterization of the biodegradable copolymers from succinic acid and adipic acid with 1,4-butanediol

Biodegradable homopolyesters such as poly(butylene succinate) (PBSU) and poly(butylene adipate) (PBAD) and copolyesters such as poly(butylene succinate-co-butylene adipate) (PBSA) were synthesized, respectively, from succinic acid (SA) and adipic acid (AA) with 1,4-butanediol through a two-step process of esterification and deglycolization. The polyester compositions and physical properties of both homopolyesters and copolyesters were investigated by ¹H– and ¹³C–NMR, DSC, GPC, WAXD, and optical polarizing microscopy. The melting point (T_m) of these copolyesters decreased gradually as the contents of butylene adipate increased and the glass-transition temperature (T_g) of these copolyesters decreased linearly as the contents of the adipoyl unit increased. PBSA copolyesters showed two types of XRD patterns of PBSU and PBAD homopolyesters. Furthermore, the biodegradation and hydrolytic degradation of the high molecular weight PBSU homopolyester, PBAD homopolyester, and PBSA copolyesters were investigated in the composting soil and NH₄Cl aqueous solutions at a pH level of 10.6. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2808–2826, 2001     

Thermotropic liquid‐crystalline polyphosphate esters containing phenolphthalein moiety

A new series of thermotropic liquid‐crystalline (LC) polyphosphate esters containing phenolphthalein as a part of their mesogen has been synthesized by a solution polycondensation method. The even‐numbered methylene spacers were varied from 2–10, and ethyl phosphate was used as a phosphorus heterogeneity. Thermal analysis showed that these polymers are stable up to 275–342°C with high char yield. All of the polymers exhibited liquid‐crystalline properties except for Polymers I and VI. Differential scanning calorimetry (DSC) confirmed the mesophase formation of the polymers. The glass transition temperature (T_g) and melting temperature (T_m) of the polymers were considerably low. A polymer containing phenolphthalein alone as a rigid segment with decamethylene spacers was also synthesized, but it did not show birefringent melt properties. These results reveal that phenolphthalein alone cannot act as a mesogen, whereas phenolphthalein phenylester can. Molecular modeling studies and conformational analysis confirmed that the steric hindrance of phenylester and the conjugation effect could explain the promotion of mesogenic behavior by phenolphthalein phenylester. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 194–200, 2004     

Synthesis and characterization of poly(ethylene‐co‐trimethylene terephthalate)s

Taking advantage of a melt polycondensation process, a series of copolyesters composed of pure terephthalate acid (PTA), ethylene glycol (EG), and 1,3‐propanediol (1,3‐PDO) were synthesized. The component, molecular weight, molecular weight distribution, and thermal properties of the copolymers were characterized. The results show that the contents of trimethylene terephthalate (TT) units in the resulting copolyesters are higher than PDO compositions in original diol. Oligomer content in the copolyesters varies with the compositions and attains a minimum value when the TT ingredient is 49.52 mol %. The glass transition temperature (T_g) of the copolyesters varies from 78.5°C for PET (polyethylene terephthalate) to 43.5°C for PTT (polytrimethylene terephthalate) and decreases monotonically with the components. The copolyesters are amorphous copolymers when TT content is in the range of 32.4–40.8 mol %, as calculated from the melting enthalpy (ΔH_m) measured via differential scanning calorimetry. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1511–1521 2006     

Synthesis and thermotropic liquid‐crystalline behaviour of novel main‐chain poly(ether ether ketone ketone)s containing a lateral tert‐butyl group

The synthesis of novel poly(ether ether ketone ketone)s containing a lateral group via the random copolymerization of 4,4′‐biphenol, tert‐butylhydroquinone and 1,4‐bis(p‐fluorobenzoyl)benzene is described. The copolymers were characterized by differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction (WAXD) and polarized optical microscopy (POM) observation. The results showed that the thermotropic liquid‐crystalline properties were achieved in the copolymers containing 30 mol% and 50 mol% tert‐butylhydroquinone, which have relatively lower melting temperatures due to the copolymerization effect. Both the crystalline–liquid‐crystalline transition (T_m) and the liquid‐crystalline–isotropic phase transition (T_i) were observable in the DSC thermograms, while the biphenol‐based poly(aryl ether ketone) has only one melting transition. The hydroquinone‐based polymer was shown to be amorphous. Thermogravimetric analysis (TGA) results showed that these copolymers are all high‐temperature resistant with higher glass transition temperature between 147 and 149 °C, and higher decomposition temperature T_d in the range 480–520 °C. © 2000 Society of Chemical Industry     

Nonisothermal crystallization kinetics and morphology of self‐seeded syndiotactic 1,2‐polybutadiene

Subsequent melting behavior after isothermal crystallization at different temperatures from the isotropic melt and nonisothermal crystallization kinetics and morphology of partially melting sPB were carried out by differential scanning calorimetry (DSC), polarized light microscopy (POM), respectively. Triple melting‐endothermic peaks were observed for the polymer first isothermally crystallized at temperatures ranging from 141 to 149°C, respectively, and then followed by cooling at 10°C/min to 70°C. Comparing with the nonisothermal crystallization from the isotropic melt, the nonisothermal crystallization for the partially melting sPB characterized the increased onset crystallization temperature, and the sizes of spherulites became smaller and more uniform. The Tobin, Avrami, Ozawa, and the combination of Avrami and Ozawa equations were applied to describe the kinetics of the nonisothermal process. Both of the Tobin and the Avrami crystallization rate parameters (K_T and K_A, respectively) were found to increase with increase in the cooling rate. The parameter F(T) for the combination of Avrami and Ozawa equations increases with increasing relative crystallinity. The Ziabicki's kinetic crytallizability index G_Z for the partially melting sPB was found to be 3.14. The effective energy barrier Δ? describing the nonisothermal crystallization of partially melting sPB was evaluated by the differential isoconversional method of Friedman and was found to increase with an increase in the relative crystallinity. At the same time, Hoffman‐Lauritzen parameters (U and K_g) are evaluated and analyzed from the nonisothermal crystallization data by the combination of isoconversional approach and Hoffman‐Lauritzen theory. The K_g value obtained from DSC technique was found to be in good agreement with that obtained from POM technique. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1479–1491, 2006     

Synthesis and characterization of copolyesters containing the phosphorus linking pendent groups

Poly(ethylene terephthalate)‐co‐poly(ethylene DDP)s [PET‐co‐poly(ethylene DDP)s], were synthesized by charging 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOP), itaconic acid, terephthalic acid, and ethylene glycol in one reactor to conduct the microaddition reaction (using H₂PtCl₆ as catalyst), esterification reaction, and polycondensation reaction. H₂PtCl₆ has demonstrated to be a highly efficient microaddition catalyst to improve the DDP conversion. The microaddition reaction of the phosphorus compound (DOP) with the itaconic acid can be proceeded at a significantly lower temperature (110°C) and results in higher conversion (> 98%). The use of the H₂PtCl₆ catalyst makes it possible to charge all the reactants in one reactor to produce high molecular weight phosphorus‐containing copolyesters without requiring the presynthesis of the DDP. These resulting copolyesters are identified by Fourier transform infrared spectroscopy, ¹H‐NMR, and differential scanning calorimetric analysis. Thermal characteristics, thermal stability, intrinsic viscosity, acid value, and rheological and mechanical properties of these copolyesters were also characterized. The presence of the bulky pendent phosphorus side groups in the copolyester tends to decrease the structural regularity and retards its crystallization. The formation of a protected char layer for the phosphorus‐containing copolyester raises the decomposition temperature of the copolyester under an oxygen atmosphere higher than that of PET. The limiting oxygen index values of all phosphorus‐containing copolyesters are all higher than 33. Higher phosphorus content results in decreasing crystallinity, lower melting temperature, lower decomposition temperature, as well as lower tensile strength, but increasing residual char after thermal degradation and higher limiting oxygen index value. The rheological behaviors of copolyesters remain similar to that of PET. The glass temperatures of copolyesters are all ∼ 77°C (76.8°–77.2°C). Incorporation of phosphorus moieties into its molecular chain has a significant effect on thermal and flame retardancy behavior. However, the crystal lattice of all copolyesters do not change with incorporation of the pendent phosphorus side group in the backbone of the copolyester. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 109–122, 1999     

Synthesis and characterization of biodegradable poly(butylene succinate‐co‐propylene succinate)s

Biodegradable polyesters such as poly(butylene succinate) (PBS), poly(propylene succinate) (PPS), and poly(butylene succinate‐co‐propylene succinate)s (PBSPSs) were synthesized respectively, from 1,4‐succinic acid with 1,4‐butanediol and 1,3‐propanediol through a two‐step process of esterification and polycondensation in this article. The composition and physical properties of both homopolyesters and copolyesters were investigated via ¹H NMR, DSC, TGA, POM, AFM, and WAXD. The copolymer composition was in good agreement with that expected from the feed composition of the reactants. The melting temperature (T_m), crystallization temperature (T_c), crystallinity (X), and thermal decomposition temperature (T_d) of these polyesters decreased gradually as the content of propylene succinate unit increased. PBSPS copolyesters showed the same crystal structure as the PBS homopolyester. Besides the normal extinction crosses under the polarizing optical microscope, the double‐banded extinction patterns with periodic distance along the radial direction were also observed in the spherulites of PBS and PBSPS. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Aromatic liquid crystalline copolyesters with low Tm and high Tg: Synthesis,characterization, and properties

In this study, a series of aromatic copolyesters P‐BPAx with lower melting temperature and higher glass transition temperature derived from hydroxybenzoic acid (HBA), 6‐hydroxy‐2‐naphthoic acid (HNA), bisphenol A (BPA) and terephthalic acid (TA) were synthesized via melt polymerization. The copolyesters were characterized by FTIR, solid state ¹³C NMR, DSC, TGA, polarized optical microscopy, X‐ray diffraction, and rheometry measurements. With addition of BPA, the resulting copolyester's melting temperature decreased from 260 to 221°C and its glass transition temperature increased from 70 to 135°C, compared with the parent copolyester P‐HBA70 (HBA/HNA copolymer). With exception of copolyester P‐BPA5.0 (225–280°C), the copolyesters could maintain liquid crystalline behavior in a broad temperature range from 230°C to higher than 410°C. The ability to form nematic liquid crystalline phase disappeared when BPA concentration became higher than 15 mol %. X‐ray diffraction analysis showed crystallinity decreased as the BPA content increased. A slightly distorted O" and a substantially distorted O′ orthorhombic phase was observed for P‐BPA2.5. Upon annealing at 220°C, the O" phase disappeared and the O′ phase became stronger gradually. Rheology study data showed the ability to process the copolyesters improved in those compositions containing <2.5 mol % BPA. Continuing to increase concentrations of BPA, they became intractable. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40487.     

A study on multiple melting of isotactic polypropylene

Multiple melting characteristics of a highly isotactic polypropylene (iPP) were studied by means of differential scanning calorimetry (DSC). Double melting characteristics were observed on melting iPP crystallized isothermally at temperatures ranging from 110 to 140°C. iPP crystallized below and above 125°C exhibited different double melting characteristics from each other. For iPP crystallized below 125°C, the single melting peak split into two peaks during slow DSC heating scans without changing the total crystallinity in the polymer. On the other hand, the double melting endotherm of iPP crystallized above 125°C seemed to come from two preexisting crystal fractions having different T_m. There existed an optimum annealing temperature range where the five-minute annealing of iPP raised T_m of the polymer significantly. The treatment also increased the crystallinity of iPP crystallized isothermally at 110°C by 12%.     

Thermophysical properties of bacterial poly(3‐hydroxybutyrate): Characterized by TMA,DSC, and TMDSC

The melting, isothermal and nonisothermal crystallization behaviors of poly(3‐hydroxybutyrate) (PHB) have been studied by means of temperature modulated differential scanning calorimetry (TMDSC) and conventional DSC. Various experimental conditions including isothermal/annealing temperatures (80, 90, 100, 105, 110, 120, 130, and 140°C), cooling rates (2, 5, 10, 20, and 50°C/min) and heating rates (5, 10, 20, 30, 40, and 50°C/min) have been investigated. The lower endothermic peak (T_m1) representing the original crystals prior to DSC scan, while the higher one (T_m2) is attributed to the melting of the crystals formed by recrystallization. Thermomechanical analysis (TMA) was used to evaluate the original melting temperature (T_melt) and glass transition temperature (T_g) as comparison to DSC analysis. The multiple melting phenomenon was ascribed to the melting‐recrystallization‐remelting mechanism of the crystallites with lower thermal stability showing at T_m1. Different models (Avrami, Jeziorny‐modified‐Avrami, Liu and Mo, and Ozawa model) were utilized to describe the crystallization kinetics. It was found that Liu and Mo's analysis and Jeziorny‐modified‐Avrami model were successful to explain the nonisothermal crystallization kinetic of PHB. The activation energies were estimated in both isothermal and nonisothermal crystallization process, which were 102 and 116 kJ/mol in respective condition. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42412.     

Study of the effect of annealing,draw ratio,and moisture upon the crystallinity of native and commercial gutta percha (transpolyisoprene) with DSC,DMTA, and X-rays: Determination of the activation energies at Tg

The transitions occurring in gutta-percha (transpolyisoprene) below the melting point were determined with DMTA and DSC. A comparison of the results obtained with these two methods showed satisfactory agreement. The thermal properties of native and commercial gutta-percha samples (T_g = 38 ± 2°C and T_m = 69 ± 3°C) were investigated, both before and after annealing (at different times and temperatures), and at environments of different relative humidities. An increase in the draw ratio also proved to enhance the percentage crystallinity (% K) and improve the thermal stability (higher T_gs and T_ms) of gutta-percha. Finally, the activation energies ΔE (33.9–40.2 kj/mol × K) at glass transition temperature were determined and correlated to the percentage content (%) of the commercial gutta-percha samples in native gutta-percha. © 1993 John Wiley & Sons, Inc.